Filaments of cellulose lower alkanoates containing amines



United States Patent FILAMENTS OF CELLULOSEjLOWER ALKA- NOATES CONTAINING AMINES Charles L. Smart, Millington, N. J., assignor to Celanese Corporation of America, New York, N. Y., a corporation of Delaware No Drawing. Application November 20, 1953, Serial No. 393,489

17 Claims. (Cl. 106-176) Organic acid ester of cellulose textile materials, such as cellulose acetate textile materials, do not normally have an afiinity for acid dyestufls and cannot be satisfactorily dyed with said dyestufis. Many treatments have been proposed for increasing the afiinity of the cellulose acetate textile materials to acid dyestuffs. These treatments have usually involved a chemical reaction between the cellulose acetate and another compound which has or may be converted to one which has a basic group or atom, such as a basic nitrogen atom, attached thereto. In order to produce the chemical reaction between the cellulose acetate and the basic nitrogen-containing compound, it is necessary to use relatively severe reaction conditions such as high temperatures and long periods of time. The use of such reaction conditions will increase the expense of preparing the cellulose acetate textile materials. It will also involve the danger of weakening the said textile materials through degradation, decoruposition, or the like.

In order to be completely satisfactory, the cellulose acetate textile materials, when dyed with acid dyestufis, should show a good wash fastness. While many of the treatments that have been proposed for increasing the affinity of cellulose acetate textile materials to acid dyestuifs will produce a product that exhibits a good afii-nity for these dyestuffs, the wash fiastness of the dyed cellulose acetate textile materials will be poor. As a result, the dyed cellulose acetate textile materials will not be suited for certain applications.

It is an important object of this invention to provide a lower alkauoate ester of cellulose textile material which I will be free from the foregoing and other disadvantages.

It is a further object of this invention to provide a lower alkanoate ester of cellulose textile material which will have a good atfinity for acid dyestulfs and which may be prepared by a simple, inexpensive process.

Another object of this invention is to provide a lower alkanoate ester of cellulose textile material which, when dyed with acid dyestufis, will be characterized by having a good wash fastness.

Other objects of this invention will be apparent from the following detailed description and claims.

According to the present invention, organic acid ester of cellulose textile materials, such as cellulose acetate textile materials, which have a good afiinity for acid dyestufls, and which, when dyed with acid dyestuffs, will exhibit a good wash fiastness, are prepared by incorporating as an additive into said cellulose acetate textile materials a small proportion of an epoxyamine or its hydrolysis product, an aminediol, or an talkanolamine containing a tertiary nitrogen atom. The incorporation of the additive into the cellulose acetate is carried out to 2,789,916 Patented Apr. 23, 1957 produce a physical mixture without substantial chemical reaction between the additive and the cellulose acetate. Surprisingly enough, however, despite the absence of substantial chemical reaction, the product obtained will not only show a good affinity for acid dyestuffs, but, when dyed with said dyestufls, will exhibit a good wash fastness. Apparently, the epoxyamine, aminediol, or alkanolamine containing a tertiary nitrogen atom or the reaction product of the epoxyamine, aminediol or alkanolamine containing a tertiary nitrogen atom with the acid dyestuif is physically trapped in the cellulose acetate in such a manner that it does not wash out of the said material during the washing procedures to which said material is normally subjected during use.

The percentage of epoxyamine, aminediol, or alkanolamine containing a tertiary nitrogen atom incorporated into the cellulose acetate textile material may range between about 1 land 4% by weight based on the weight of the cellulose acetate. With these percentages of the additive, there will be no appreciable changes in the physical properties of the textile materials, such as their strength, elongation and the like, which changes could occur if higher percentages of the additive were used. Lower percentages of the [additive will not impart a sufficiently high afiinity to acid dyestuffs to the textile ma terials.

Examples of suitable epoxyamines that may be employed as additives include 1-amino-2,3-epoxypropane, lamino-3,4-epoxybutane and 1-monoethylamino-2,3-epoxypropane. A specially valuable group of epoxyamines that may be employed as additives are the epoxyamines con taining a tertiary nitrogen atom including, for example, 1-dimethylamino-2,3-epoxypropane, 1-diethylamino-2,3- epoxypropane, 1-dipropylamino-2,3-epoxypropane, l-diisopropylamino 2,3 epoxypropane, l-dibutylramino-Zjepoxypropane, 1-methylpropylamino- 2,3 epoxy-propane Ian-d l-dimethylamino-3,4-epoxybutane. In addition to the dialkylamin epoxy compounds there may also be employed other epoxyamines containing a tertiary nitrogen atom including, fior example, 1-N,N-diphenylamino-2,3- epoxypropane, 2-methyl-5-epoxypyridine and l-morpholino-2,3-epoxypropane. Examples of suitable aminediols that may be employed as additives include, for example, the hydrolysis products of the epoxyamines listed above. Thus, there may be employed as additives lamina-2,3- p roplanediol, l-amino-3,4-butanediol, and l-monoethylamino-2,3-propanediol. As with the epoxyamines, a specially valuable group of aminediols that may be employed as additives are the aminediols containing a tertiary nitrogen atom including, for example, 1-dimethylamino-2,3-

propanediol, 1-die-thylamino-2,3propanediol, 1-dipropylamino-2,3propanediol,

1-diisopropylamino-2,3propanediol, l-dibutylamino-2,3propanediol and l-dimethylamino-3,4-butanediol. In addition to the dialkylamino diols there may be employed other aminediols containing a tertiary nitrogen atom including, for example, l-N,N- diphenylamino-Z,3-propanediol, 2-rnethyl-5-( 1,2 ethandiol)pyridine and 1morpholino-2,3propanediol. Alkanolamines containing a tertiary nitrogen atom that may be employed as additives include, for example, bis-diethylamino-propanol-Z, bis-dimethylamino-propanol-Z, bis-diis-opropylamino-propanol-2, bis-dibutylamino-propanol-2, bis-methylpropylamino propanol 2, bis-diphenylaminopropanol-Z, bis-dipropylamino-propanol-Z and bis-dimorpholino-propanol-Z. The epoxyamines are, in general, somewhat superior to the aminediols and alkanclamines in imparting wash fastness to dyed textile materials. However, textile materials containing the aminediols and alkanolamines have sufiicient wash fastness for many purposes.

The additives may be incorporated in the cellulose acetate textile materials in any desired manner. For ex ample, the additives may be added in the desired proportions to a solution of the cellulose acetate, which soluti-on may aduantageously comprise the spinning dope from which the cellulose acetate textile materials will be produced. Alternately, a concentrated solution of the additive may be injected into a spinning dope, comprising a solution of the cellulose acetate in a solvent, as the spinning dope: is pumped or otherwise forced to a spinnerette. The incorporation of the additive into a spinning dope constitutes a simple :and inexpensive way to obtain a uniform mixture of the additive and the cellulOSe acetate and is therefore preferred. Other Ways in which the additive may be incorponated into the cellulose acetate are by treating the cellulose acetate flake with a solution of said additive in a liquid which is a non'soivent for the cellulose acetate, such as benzene. The treatment may be carried out at elevated temperatures of between about 40 and 80 C. for between about and 120 minutes, or in the presence of a swelling agent for the cellulose acetate, to obtain a uniform diffusion of the additive through the cellulose acetate. The additive may also be incorporated into the cellulose acetate after the latter has been converted into av yarn or fabric by treating said yarn or fabric with a solution of said additive in a liquid which is a non-solvent for the cellulose acetate, such as benzene. As in the case of the treatment of the flake, the treatment of the yarn or fabric may be carried out at elevated temperatures of between about 40 and 80 C., for between about 5 and 120 minutes or in the presence of a suitable swelling agent for the cellulose acetate to obtain a uniform diffusion of the additive through the cellulose acetate.

Acid dyestufis with which the additive-containing cellulose acetate may be dyed to produce dyeings of good wash fastness include Alizarrine Sky Blue B. S. (C. I. 1088), Xylene Milling Yellow 2GP and Azorubinol 3GP. The said dyestuffs may be applied to the additive-containing cellulose acetate textile materials in conventional mannor.

in addition to the additives specified herein, the eel lulose acetate textile materials may contain other materials such as pigments, dyes, nacreous materials, gas fading inhibitors, ultra-violet light absorbents and the like capable of altering the appearance or properties of the final products.

Organic acid ester of cellulose materials other than cellulose acetate into which the additives of this invention may be incorporated include, for example, cellulose propionate, cellulose butynate, cellulose acetate propionate and cellulose acetate butyrate.

The following examples are given to illustrate this invention further:

Example I There is added to a spinning dope, comprising a solution of cellulose acetate in acetone, 2% by weight on the weight of the cellulose acetate, of l-diethylamino- 2,3-epoxypropa-ne, the spinning dope tumbled for 1 hour, and spun to form a yarn. A fabric formed from said yarn is dyed at 90 C. for 1 hour in an aqueous dyebath containing 0.5 by weight of formic acid and 2% by weight on the Weight of the fabric of A-lizarine Sky Blue BS (45% oil color). The dyed yarn has a good blue color and does not stain or show loss of color when heated at 72 C. for 1 hour in an aqueous solution of 1% soap and 1% sodium carbonate. Cellulose acetate yarn to which no additive has been :added is not dyed with this dyebath.

When the cellulose acetate yarn is dissolved in acetone and the cellulose acetate recovered by reprecipitation, it shows on analysis less than 0.01% nitrogen, indicating that there has been substantially no chemical reaction between the epoxyamine land the cellulose acetate.

The physical properties of the additive-containing yarn 4 do not difier appreciably from those of a cellulose acetate yam to which no additive has been added.

Example 11 There is added to a spinning dope, comprising a solution of cellulose acetate in acetone, 2% by weight, on the weigh-t of the cellulose acetate, of 3-diethylamino-l,2- propanediol, the spinning dope tumbled for 1 hour, and spun to form a yarn. A fabric formed from said yarn is dyed at C. for 1 hour in an aqueous dyebath containing 0.5% by weight of formic acid and 2% by weight on the weight of the fabric of Xylene Milling Yellow 2GP (50% of oil color). The dyed yarn has a good yellow color and does not stain or show loss of color when heated at 72 C. for 1 hour in an aqueous solution of 1% soap and 1% sodium carbonate.

The physical properties of the a-dditive-containi-ng yarn do not differ appreciably from those of a cellulose acetate yarn to which no additive has been added.

Example II] There is added to a spinning dope, comprising a solution of cellulose acetate in acetone, 2% by weight, on the weight of the cellulose acetate, of bis-diethylaminopropanol-2, the spinning dope tumbled for 1 hour, and spun to form a yarn. A fabric formed from said yarn is dyed at 90 C. for 1 hour in an aqueous dyebath containing 0.5% by weight of formic acid and 2% by weight on the weight of the fabric of Azorubinol 3GP (40% oil color). The dyed yarn has a good red color and doe not stain or show loss of color when heated at 72 C. for 1 hour in an aqueous solution of 1% soap and 1% sodium carbonate.

The physical properties of the additive-containing yarn do not differ appreciably from those of a cellulose acetate yarn to which no additive has been added.

It is to be understood that the foregoing description is given merely by way of illustration and that many variations may be made therein Without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent is:

l. Textile material comprising filaments of cellulose lower alkanoate containing as an additive a compound of the group consisting of epoxyamines in which the epoxy oxygen is attached to aliphatic carbon atoms, tertiary aminediols in which the hydroxyl group are on aliphatic carbon atoms and tertiary monohydroxy alkanolamines in which the hydroxyl group is on an aliphatic carbon atom, said compound containing only carbon, hydrogen, nitrogen, and oxygen atoms, said additive acting to increase the alfinity of said textile material to acid dyestuffs.

2. Textile material as set forth in claim 1 in which said cellulose lower alkanoate is cellulose acetate.

3. Textile material as set forth in claim 2 in which saidadditive is an epoxyamine.

4. Textile material as set forth in claim 3 in which said additive is a tertiary monoepoxyrnonoamine.

5. Textile material as set forth in claim 2 in which said additive is an aminediol.

6. Textile material as set forth in claim 5 in which said additive is an aminediol having its hydroxyl groups on adjacent carbon atoms.

7. Textile material set forth in claim 2 in which said additive is a tertiary monohydroxy alkanolamine.

8. Textile material as set forth. in claim 2 in which the proportion of said additive is about 1 to 4% based on the weight of the cellulose acetate.

9. Textile material as set forth in claim 8 in which said cellulose acetate is acetone-soluble and said additive is in physical admixture with said cellulose acetate as evidenced by the fact that on dissolution of said cellulose acetate textile material in acetone and reprecipitation of the cellulose acetate the reprecipitated cellulose acetate contains less than 0.01% nitrogen.

10. Textile material as set forth in claim 9 in which said additive is 3-diethylamino-1,2-propanediol.

l1. Textile material as set forth in claim 9 in which said additive is bis-diethylaminopropanol-Z.

12. Textile material as set forth in claim 9 in which the additive is l-diethylamino-2,3-epoxypropane.

13. Textile material as set forth in claim 2, said textile material being dyed with an acid dyestuff.

14. Acetone soluble cellulose acetate textile material containing in physical admixture with the cellulose acetate as an additive between about 1 and 4% by weight based on the weight of the cellulose acetate of l-diethylamino- 2,3-epoxypropane, said textile material being dyed with an acid dyestulf.

15. As a spinnnig dope for the production of filamentary material a solution in a volatile solvent of a cellulose lower alkanoate containing as an additive an epoxyamine, in which the epoxy oxygen is attached to aliphatic carbon atoms, said epoxyamine containing only carbon, hydrogen, nitrogen and oxygen atoms, said additive acting to increase the afiinity to acid dyestuffs of filamentary material produced by the spinning of said dope.

16. As a spinning dope for the production of filamentary material a solution in a volatile solvent of a cellulose lower alkanoate containing as an additive a tertiary monoepoxymonoamine containing only carbon, hydrogen, nitrogen and oxygen atoms, the epoxy oxygen of said epoxyamine being attached to aliphatic carbon atoms, said additive acting to increase the affinity to acid dyestuffs of filamentary material produced by the spinning of said dope.

l7. Acetone-soluble cellulose acetate textile material containing as an additive a tertiary epoxyamine containing only carbon, hydrogen, nitrogen and oxygen atoms in which the epoxy oxygen is attached to aliphatic carbon atoms, said additive acting to increase the aflinity to acid dyestufis of filamentary material produced by the spinning of said dope.

References Cited in the file of this patent UNITED STATES PATENTS 1,880,514 Staud et al. Oct. 4, 1932 1,977,253 Stallman Oct. 16, 1934 2,131,120 Schlack Sept. 27, 1938 2,199,927 Underwood May 17, 1940 2,240,151 Wampner Apr. 29, 1941 2,371,768 Malm et a1 Mar. 20, 1945 2,425,351 Sharphouse Aug. 12, 1947 2,522,469 Sweeney Sept. 12, 1950 

1. TEXTILE MATERIAL COMPRISING FILAMENTS OF CELLULOSE LOWER ALKANOATE CONTAINING AS AM ADDITIVE A COMPOUND OF THE GROUP CONSISTING OF EPOXYAMINES IN WHICH THE EPOXY OXYGEN IS ATTACHED TO ALIPHATIC CARBON ATOMS, TERTIARY AMINODIOLS IN WHICH THE HYDROXYL GROUPS ARE ON ALIPHATIC CARBON ATOMS AND TERTIARY MONOHYDROXY ALKANOLAMINES IN WHICH THE HYDROXYL GROUP IS ON AN ALIPHATIC CARBON ATOM, SAID COMPOUND CONTAINING ONLY CARBON, HYDROGEN, NITROGEN, AND OXYGEN ATOMS, SAID ADDITIVE ACTING TO INCREASE THE AFFINITY OF SAID TEXTILE MATERIAL TO ACID DYESTUFFS. 